Corrosion studies of a chromium steel in imitated seawater

A series of in-door experiments was performed to get some insight into the corrosion behavior of a commercial alloy Fe-12% Cr (3CR12) exposed to imitated seawater. Applying different analytical methods, the main corrosion process was found to be the formation of flakes on the surface which, peel off after they have reached a certain size. Some Cr is dissolved in the solution, its relative concentration with respect to Fe is higher than in the bulk material. The flakes consist mainly of mixed oxihydroxides of the type FeOOH containing some Cr and Mg. The oxidic layer on the interface is very thin, behaves essentially stationary with a slight growth of about 0.05 nm/day. It consists of Cr oxide with some inclusions of Fe and Mg and is not of a chromite type. Immediately below this oxidic layer, the metallic substrate exhibits a thin layer depleted in Cr and behaving like α-Fe (bcc). As compared with stainless steel, potentiostatic current vs. time records at anodic potentials below the pitting potential indicate a very different stability of the surface films for 3CR12. The kinetics of the passive layer formation on 3CR12 was found to follow a parabolic law initially and to change later (after 10...100 seconds in deaerated solution and even earlier in aerated solution) to a linear law. After some time, pitting corrosion and/or cracks due to internal stresses play the dominant role. Cr does not form a protective oxidic layer. The surface morphology of samples exposed at -200 mV for 20 and 80 minutes has been studied by scanning electron microscopy and scanning Auger microprobe. The results reflect the competing formation of oxidic layers and pitting, the participation of Cr in the dissolution process. It is also suggested that Mg, which is a component of the solution was incorporated into the rust and some Mg was also found on the metallic surface. (author)